Process of deinking printed paper



Patented Sept. 5, 1933 are!) STATES PATENT orrlcs mess-i2 PROCESS OF nsmxmc PRINTED PAPER Elton a. Darling, Elgin, 111., assignor to Mariner & Hoskins, Inc., Chicago, 111., a corporation of Illinois ,No Drawing.

Application November 14, 1931' Serial No. 575,151

is Claims. (CL sa -1s) The present invention relates to a novel process for de-inking coated as well as uncoated printed paper, whereby the ink as well as any fillers droxide having a pH of 9.0 to 12.6, followed by treatment of the paper by beating it ,in the same solution, so as to bring about a substantial disintegration, after which the ink and fillers are liberated and brought into suspension by the addition of a suitable emulsifying agent.

Another object of the invention is to remove printink ink from paper in an alkaline medium by the aid of an emulsifying agent comprising a.

water-soluble sulphonated petroleum hydrocarbon product.

Still a further object of the invention is to treat news stock and other unfilled papers in an alkaline medium with an emulsifying agent of the type above mentioned, with the addition of a finely divided suspensible insoluble medium having a particular attraction for loosened ink, whereby the ink will deposit itself upon said medium in preference to the cellulose fibers from whichit has been released. I

Other objects of the invention will become apparent from the description and claims to follow hereinbelow.

Many processes for the de-inking of paper have I ing for their action upon rather strong chemicals which either dissolve the vehicle of the ink or else destroy it by a process akin to saponification, so as thereby to liberate the carbon and other pigments constituting the color of the ink. In such a process, however, the chemicals em ployed are of such strength that they will deleteriously afiect the cellulosic fibers of which the paper is constituted, thereby injuring the same and rendering the final de-inked product by no means as desirable as fresh paper pulp. Furthermore, the paper which has been de-inked by means of strong alkalies or saponifying agents yields a de-inked paper stock that is relatively dark and which either requires an abnormal amount of bleaching to bring it to acceptable whiteness or, under certain circumstances caused by a redepcsition of colloidally dispersed carbon ing thereof.

particles upon the paper, is simply unbleachable and can therefore be used only for manufacturing cheap cardboard or pulp articles.

It has already been proposed to employ various kinds of soap for the liberation of ink from paper, but in most instances this involves the employment of either high temperatures or solutions of such strength that the above enumerated inconveniences are unavoidably a part of the process.

Research undertaken by the inventor of the present process has demonstrated that there are certain alkalies or alkaline reacting compounds which are of specific value in the treatment of paper for the purpose of separating therefrom printing ink pigment and such fillers as may have been used in the coating of the paper or the siz- In most de-inking processes a particularly important factor has been overlooked,

namely, the recovery of the fiber in substantially resulting mixture with such emulsifying agents as will cause the fibers to segregate by themselves, while the fillers, pigment and ink form a complex which under the conditions of operation has no afl'inity for the cellulosic fibers, so that physical separation by means of filtration of the, fibers from such suspended material as fillers and ink pigment is rendered commercially possible.

In case of the treatment of papers which do not contain any fillers, it has been found advisable in practicing the process of the present invention deliberately to add to the paper undergoing treatment inert flllers or mineral substances which have this affinity for the ink pigment, so as to insure the production of a substantially white, practically unharmed cellulosic paper pulp which may immediately be re-employed for the manufacture of fresh paper of a grade which will not be inferior to the original paper stock.

Concisely expressed, the process comprises treating printed paper with a solution containing sodium hydroxide and either sodium metasilicate or trisodium phosphate, the solution being of such a strenght that it has a hydrogen ion concentration equivalent to pH 9.0 to 12.6.

While sodium hydroxide may be used alone, it

is preferred to employ a combination oi? sodium hydroxide and. metasilicate or sodium hydroxide and trisodium phosphate or, if desired, all three oi" these substances. However, the hydrogen ion concentration of the solution should lie within the range above given. The paper is beaten in a suitable paper beater with a solution of the composition just stated, the beating being surlioient to tear the paper into small shreds or particles so as to insure a thorough treatment and promotion of the ink by the solution. During this portion of the process the vehicle of the ink is softened, but the ink will still adhere to the paper, having apparently an opposite charge to that of the paper particles themselves.

After "seating for some time, there is added an emulsifying agent which causes separation 01 the ink from the paper, most prooably by causing the ink to assume opposite electrical charge so as to become repellent to the paper fibers. As an emulsifying agent, there may be employed either ordinary soap or a sill pl'ioooterl oil made from a hydrocarbon base such, for as the oil made and described the patents to Harold T. ldaitlancl, Nos. 1,4

l, l25,s93; 1,425,884 and lei-25am ot pliooated hydrocarbon oil has the peculi or water miscible and is a po emulsifying agent loot does not cause the to learn does ordinary soap. It therefore particular advantages this field, because not :cause overflow or undue frotl'liog or" the mixture while being agitated.

oi lie fibers from the filers and six? terials Well as the ink pigment, so t t beooiries possible, after a short additional period oi beating, to run the mixtiroe oi paper and solo tion in which it is suspended over a ii. or sieve which is fine enough to retain the io dividual ii oers loot sufficiently coarse to allow the eseape oi the solution and the finely divided :iillers and ink pigment which pass ofl the solution, leaving the paper fibers behind.

its an esemplificetiori of the preferred prop-0% tionsoi material to be employed, it may be stated that the paper is treated with about loll parts or Water to each part of paper in an ordinary paper beater orhollonder, the said water containing sufiicient of the sodium hydroxide, sodium metasilioate and/or trisodium phosphate to give it the desired hydrogen ion concentration oi pH to 12:8. The duration oi this beating is prererataly about one hour. At the end of that time there is added for each 5 grams of paper present lo ml. or" a 1% soap solution or a 1% solution of the sulphooated oil in water, which is equiv= alent to 1/10 gram or soap to 5 grams of pap-er, or in the ratio of 1 part of soap or siilplioriated oil to every so parts or" paper, In other words, when treating a ton of paper, there would lie re quired 1/50 too or to pounds of soap or the said oil. The said suiphooated oil is quite dispersiloie in water and produces a. sort of milky emulsion.

After the addition oi the soap or oil, the beating is continued for about 20 minutes, until it is seen that the fibers have quite well separated from the fillers in the paper and the ink pigment. If the paper that is being treated does not contoiri any fillers, it is advisable, although not ob solutely essential, to add a finely divided in organic material such asfiriely powdered gypsum or land p'iwter, or a colloidal clay such as bentooits. The amoimt of smell fillers added :fortlois moss-rs purpose may Toe on the order of from iii to 25 pounds per ton of umilled paper, such as z1esvsprint, undergoing treatment. After adding this extraneous mineral matter, the beating is prei= erably continued a further 20 minutes so as to insure the gathering or the ink pigment upon the said mineral matter, so that it cannot redeposit upon the cellulosio fibers.

either event, that is, when treating either coated or micoated paper, the material is now ready for filtration to separate the cellulosic iibers from the pigment and fillers. This is ac oomplish'ed by running it over a coarse sieve hav ixig meshes enough to hold the fibers but sufficiently coarse to let the fillers, ink pigment and dispersed ink vehicle pass through with the solution. It is preferred to do this without any suction, and the most advantageous ma'mier 0:? doing it is to pass the material over an ordinary screen such as is well known in the paper -mak lug It is not advisable to employ any great degree oi suction, as this tends to mat down the floors and thereby causes physical entrapment of the pigment and fillers.

After the solution containing the suspended pier-merit and fillers, etc. is passed through the soreen, tlie celltlosie titers then lse washed so as to sure the removal of any .ual fillers and meet, this lasing done ei sea" on screen its-elf preferably, by risierriog the wet mass or oelloiosio pulp to a f so]. eoriteirlri clear tvater and thereupon t Wing this new mixture onto the screen. i es where. the Water is hard and when Io looali soop so, toned the water so as to prevent the formation of insolrible oloioro soap, which, formed, would deposit it ell" upon the tillers and cause them to lose tiles.- brilliant wlqiite color. it such an alisoiine washing solutioo is employed, does riot necessarily imply a tvaste oi material, as filtrate obtained from this washing may, alter oorrection for its hydrogen ion concentrat time, be employed for the met step in treat? ment of a subsequent batch of printed paper. However, it the sulploomated oil is employed, this precaution will not be necessary. is, oi ooiirse, within the scope of the iovezotiozo to employ liotli the soap and the oil, using reduced quantities of each, so that the combined of the oil and soap amounts to the satio oi about i to 5 9 (1250) as based upon oil-soap seed paper respeotively.

In any event, and psrtictdsriy alkali is used io'tiae water, the paper iiber is then mother "washed ster so as to remove the residual alkalinity thereof and produce a polo suitable for ties of new paper or paper product.

Ordinarily, emplo the present process, the obtained is sorrloieotly white for commercial purposes, but it or course, not constitute departure from the present iriven= tion to "bleach time resulting pulp ivy any of the Well known means.

The present process has iieeri partleolorly use fill in the removal of colored priritios' ink from highly coated magazine stools and similar papers, it being well known that tile removal oi modem rotogravure and process presents a problem dificult of solution and a problem which was never presented to prior inventors, as in the past ordinary printing based upon merely a lin seed oil base were the most commonly employed,

s used, is advisable to employ a water or else to add sold-elem elzsali to iso Mil

12.6, it will be advisable to use a somewhat lower temperature, say 160 F. (or from 60 to 75 C.).

Heating the solution in this manner accelerates the action, but the process will work evenv at room temperatures, provided the agitation is sufficiently prolonged.

1. The process of separating the cellulosic fibers of filled and printed paper from the printing ink and fillers therein contained which comprises beating the paper in a solution containing an alkaline reacting compound selected from the group consisting of sodium hydroxide, sodium metasilicate and trisodium phosphate in' such proportions as to render said solution alkaline to the extent of having a hydrogen ion concentration of from pH 9.0 to pH 12.6 until the paper has been substantially disintegrated, and thereupon adding to the suspension thus formed a small amount of an emulsifying agent, continuing the beating for a short period of time, and thereupon filtering the suspension through a sieve fine enough to retain the cellulosic fibers but coarse enough to pass the fillers and ink particles.

2. The process of separating the cellulosic fibers of filled and printed paper from the printing ink and fillers therein contained, which comprises beating the paper in afsolution containing an alkaline reacting compound selected from the group consisting of sodium hydroxide, sodium metasilicate and trisodium phosphate in such proportions as to render said solution alkaline to the extent of having a hydrogen ion concentration of from pH 9.0 to pH 12.6 until the paper has been substantially disintegrated, and thereupon adding to the suspension thus formed a small amount of soap, continuing the beating for a short period of time, and thereupon filtering the suspension through a sieve fine enough to retain the cellulosic fibers but coarse enough topass the fillers and ink particles;

3. The process of separating the cellulosic fibers of filled and printed paper from the printing ink and fillers therein contained, which comprises beating the paper in a solution containing an alkaline reacting compound selected from the group consisting of sodium hydroxide, sodium metasillicate and trisodium phosphate in such proportions as to render said solution alkaline to the extent of having a hydrogen ion concentration of from pH 9.0 to pH 12.6 until the paper has been substantially disintegrated, and thereupon adding to the suspension thus formed a small amount of a water-dispersible sulphonated hydrocarbon oil, continuing'the beating for a short period of time, and thereupon filtering the suspension through a sieve fine enough to retain the cellulosic fibers but coarse enough to pass the fillers and ink particles.

4. The process of de-inking printed paper, which comprises beating the same in a solution having a hydrogen ion concentration of between pH 9.0 to pH 12.6 until substantial disintegration of the paper has been efiected, thereupon add- What it is desired to protect by Letters Patent ing an emulsifying agent and an inert finely divided filler, continuing the heating for a short period of time, and thereupon filtering the resulting suspension through a sieve fineenough to retain the fibers of the paper but coarse enough to pass the particles of loosened printing ink and added filler.

5. The process of de-inking printed paper, which comprises beating the same ina solution having a hydrogen ion concentration of between pH 9.0 and pH 12.6 until substantial disintegration of the paper has been efiected, thereupon adding soap and an inert finely divided filler, continuing the beating for a short period of time,

and thereupon filtering the resulting suspension.

through a sieve fine enough to retain'the fibers of the paper but coarse enough to pass the par ticles of loosened printing ink and added filler.

6. The process of de-inking printed paper, which comprises beating the same in a solution having a hydrogen ion concentration of between pH 9.0 'and pH 12,6 until substantial disintegration of the paper has been effected, thereupon adding a water-miscible sulphonated hydrocarbon oil and an inert finely divided filler, continuing the beating for a short period of time, and thereupon filtering the resulting suspension through a sieve fine enough to retain the fibers of the paper but coarse enough to pass the particles of loosened printing ink and added filler.

'7. The process as defined in claim 1, wherein the material remaining on the sieve after filtration is sludged upwith an .alkaline solution, refiltered, and washed.

8. The process of de-inking printed paper, which comprises comminuting the same while suspended in a solution of sodium hydroxide and sodium metasilicate having a hydrogen ion concentration of from pH 9.0 to pH 12.6, thereupon adding soap to the resulting suspension, beating the mixture thus formed, and then filtering the same through a sieve fine enough to retain the cellulosic fibers of the paper butcoarse enough freely to pass the loosened ink particles and inert fillers which had been contained in said paper.

9. The process of de-inking printed paper, which comprises comminuting the same while suspended in a solution of sodium hydroxide and sodium metasilicate having a hydrogen ion con- I centration of from pH 9.0 to pH 12.6, thereupon adding a water-miscible sulphonated hydrocarbon oil to the resulting suspension, beating the mixture thus formed, and then filtering the same through a sieve fine enough to retain the cellulosic fibers of the paper but coarse enough freely to pass the loosened ink particles and inert fillers which had been contained in said paper.

10. The process of de-inking printed paper, which comprises comminuting the same while suspended in a solution of sodium hydroxide and sodium metasilicate having a hydrogen ion concentration of from pH 9.0 to pH 12.6, thereupon adding soap and a water-miscible sulphonated hydrocarbon oil to the resulting suspension, beating the mixture thus formed, and then filtering the same through a sieve fine enough to retain the cellulosic fibers of the paper but coarse enough freely to pass the loosened ink particles and inert fillers which had been contained in said paper.

11. The process of de-inking printed paper,

which comprises comminuting the same while adding soap and insoluble finely flividedminemi matter to the resulting suspension, the

mixture thus formed, and. then filtering the semethrough a sieve fine enough to retain the oeilu= losic fibers of the paper but coarse enough zfi'eeiy to pass the loosened ink particles and inert fiiiers which had been contained in said paper.

12. The process of tie-inking printed paper,

which comprises eomminutiiig the same While suspended in a solution of sodium hydroxide end sodium metesilioete having a hydrogen ion com centretion of from pH 9.0 to pH thereupon adding a Water-miscible sulphonoted hydrocarbon oil, seep and. insoluble finely divided mineral matter to the resulting suspension, nesting the mixture thus formed, and then filtering the through a sieve fme enough to retefm eeiiti iosie fibers oi the paper but coarse enough freely to pass the loosened ink particles and inert fillers which had. been contained in said paper.

13. The process of de-inking printed paper which comprises first subjeeting the some to the action of on equeous solution having a hydrogenion concentration between pH 9.9 and 1.8, then adding to the resulting suspension an emulsifying agent that causes repeiiance between the fibers of the paper and the particles of the ink pigment, thereupon separating the 'fibezrs from. the pigment and solution by fil ratien, sludging up the thus formed fiber mess with alkaline solution, separating the fibers from said letter solution, and washing them substentieliy fi e from ELTON EARNING. 

